Method for purifying gas mixtures



Oct. 21, 1941.-

Filed April 7, 1938 fin nces .suL- nma 007-457 7'0 WE R 8 l I v 2 m 6 A 2 1 m2 :I l W a n v .n k a 5% m 71W 2 o] 4 n 0 m7 v .3 2. v 8 I w ,..|I 1 2 H W .R I G I Y W...// m 2 Llquoz Luvs Patented other, rear idbiitilh stares j resser ferries W'EHQD FOR PU i' l\ GAS m'EURES George L. Matheson, Union, N. 91, assignor to Standard Oil Development Company, a come:

ration of Delaware dppiication Aprii i, 193%, Serial No. 2%,599

d Claims.

The present invention relates to the purification of gas mixtures and more specifically to a g method for removing weakly acid constituents from fuel and other gases. This invention will be fully understood from the following description and the drawing which illustrates one means for carrying out the process.

The drawing ism. semi-diagrammatic sketch in elevation of an apparatus arranged for the carrying out of the present process showing the absorption of the weakly acid constituents from the gas mixture and the recovery of the absorption menstruum.

In the following description the process as adapted to the removal of hydrogen sulphide from fuel gases by means of a concentrated solution of sodium dichlorphenate is given for pur-, pose of illustration. it will be understood that other weakly acid gases may be removed from other gas mixtures by this process and for this purpose other absorption media may be substituted for sodium'dichlorphenate as will be made clear below.

into two portions by a plate 2] which is similar Y in the chamber it.

downwardly and vapor upwardly .through the tower. The tower may be conveniently divided a by a closed steam coil ii. A refluxing coil it may be placed in the upper end of the tower it and a cooling medium such as cold water'may be passed through the coil to condense and re- The gas mixture is supplied by gas main i to a scrubbing means i; which is conveniently in the form of a tower fitted with'contact means 3.

' The absorbent material is forced into the top of the tower by means of a line d. The tower may be operated at any convenient pressure, for example, at atmospheric pressure or at higher pressures if available, but it will be understood that the process can work at reduced pressures as well. The gases leave the tower by a line 5,

and may be passed through a series of short towers or bottles supplied with caustic soda and designated by numerals t and 1. These are not necessary to the process but are desirable in order to remove all trace of the gas impurities and of sodium dichlorphenate which may be .carried over from the tower, especiallyif the rate of now of gas is high. The purified gases are utilization. As the solution of the sodium iii chlorophenate or its equivalent passes downward ly through the tower 2 in countercurrent contact with the impure gas, the weak acid fconstituents' of the gas are absorbed and replacefdichlorphenate from its salt. Thedichlorphenate is pre cipitated in a fluid form and the two immiscible 7 liquids, the aqueous and'the dichlorphenate, flow together through the tower and are conducted by pump 9 and pipe Iii to the recovery system. Pipe it dischargesinto the column of tower still H which may be fitted with'plates l2, with turn to the tower all the dichlorphenate, and the greater part of the water which may be vaporized during the heating operation. It is also of ad=-, vantage to acid sodium dichlorphenate by means of recirculating pump 23 through pipe 28, in the form of a strong, aqueous solution or mixture which flows with ease through the pipe. Pipe it carries oi the hydrogen sulphide to be burned or utilized as desired.

The stripped liquor leaving the still by means of pipe 20 passes through cooler 2! into a separator 22. This separator is not required if a tower fitted with a plate 27 as shown is used. It

is especially desirable, however, where an ordinary tower is provided without a plate such as 2'? and, the settling drum it. Make-up sodium i now conducted by the main 8, to the point of r dichlorphenate may be added by pipe 26. Theoretically, there should be no loss of sodium dichlorphenate since the sodium dichlorphenate is regenerated during the process, but in practice it is found that small losses occur probably due to absorption of strong acid gases such as S02, and that this is the most convenient place for .making up these losses. An aqueous solution of the alkali salt is drawn off from the lower partof'the separator 22 and is returned to tower i byline 25 and pump 26.

v Inthe operation or this process, it is found that the chlorinated phenolic salts of strongly basic metals, such as alkali metals which form water soluble sulfides, are highly desirableabsorption ,means for weakly acid constituents, such as hydrogen sulfide, carbon dioxide, hydrocyanic acid and sulfur dioxide or the like which boom in fuel the ordinary means for allowing liquid to pass and other industrial gas mixtures. Strong acid gases, such as $03 are dissolved but cannot be expelled by heating and this process is, therefore, not adapted to the removal of such gases. Other Iective as absorption means, particularly substituted phenols in which a hydrogen had been substituted by a negative group with an increase in acidity of the hydrogen of the hydroxyl group of the phenols. The negative groups that may be used are nitros, hydroxyls, halogens, sulfides, sulfonates, etc. Halogenated alkylated substitution products of phenol may likewise be used with advantage as well as other alkylated substitution products of phenol in which one of the negative groups had been substituted in place of a hydrogen. Mixtures of these compounds may be used alone or in admixture with other absorbents,

' heating maybe carried out as shown in the drawing under rectifying or refluxing conditions, and in this case it is desirable to maintain the still somewhat above 100 C. that, is to say, at the boiling point of the solution which is usually from 105 to about 115 C. The upper end 0! the.-

column is heldat a temperature of about 90 F. or even lower so that substantially no sodium dichlorphenate is removed and the dry gas leaves the tower without removing a substantial amount of water. It is highly desirable to provide an excess of the sodium dichlorphenate in the upper part of the column and this may be done by the tower as shown in the drawing with the plate 21 and the means for using and separating the two layers or it can be accomplished merely by add-.

ing an excess of sodium dichlorphenate by pipe 24 which is subsequently separated and returned by separator 22. It will be understood that any equivalent form of apparatus may be used instead of the apparatusshown. 4

' It is not' necessary to conduct the stripping operation under rectifying conditions, and it desired it can be done by simply heating in an ordinary still to boiling point but under theseconditions part of the water and some of the phenol will be carried over and must be condensed and recovered. Open steam may be injected into the base of the tower to assist stripping but care should be taken not to unduly dilute the scrubbing liquor. Inert gas can be used in place of steam. if it is not desirable to recover the acid gas in concentrated form.

This process may be used for a great many different weakly acid gas constituents among which carbon dioxide, hydrogen sulphide, sulphur dioxide and hydrocyanic acid are the most common, but other gases of substantially the same acid strength may berecovered as will be understood. In the processit is preferred to use a relatively strong aqueous solution of the sodium, or potassium dichlorphenate or its solves a somewhat greater proportion of hydro 4 gen sulphide than .can besubsequentiy evolved simply by heating, but the fact that a certain equivalent. When sodium dichiorphenate is first used it dis- 2,259,901 derivatives of phenol were found to be very e1"- BAsrs': 1 Gannon or Aasoannnr All solutions saturated with 100% 1128 at 75 F.

Triethanolamine Crude sodium 50% by weight sodium plum phenate Total Total Total heat for heat for gg g heat for at s. c. at s. 0. t??? at s. o. fig desorbed B; L dcsorbed B desorbed Sodium mono- Sodium dichlorphen- Crude sodium chlorphenate ate chlorinated phenate Total Total Total heat for heat for heat for at s. c.- figff at s. o. i-m at s. 0.. ggf desorbed B. u desorbed B t u desorbed B t u 1. 1c 1190 q 0. as 323 0. so 91 2. 38 1880 1. 09 492 1. 15 161 3. 73 2420 L 67 564 1. 225 4. 2750 2. 29 629 2. 42 281 6. 00 3430 2. 89 678 3. 03 367 7. 20 4225 3. 46 741 3.64 471 8. 40 5860 4. 04 843 4. 24 576 9. 45 7280 4. 61 1000 4. 86 691 5. 19 1110 5.45 808 5. 80 1280 6. 05 953 This invention is not to be limited to any theory of the particular chemical reactions which may be supposed to occur during the absorption, or recovery steps, nor to the removal of any particular weakly acid gas constituent, nor, indeed, to any particular absorption means, but

only to the claims in which it is wished to cover this invention as fully as is permissible by the prior art.

I claim:

1. A processor removing hydrogen sulfide, carbon dioxide and the like from a gaseous mixture containing the same which comprises scrubbing the gas with an aqueous solution of an alkaliforming' metal and a dichlorphenol, the phenol being in excess of the stoichemical equivalent of the alkali to absorb hydrogen sulfide, carbon dioxide and the like from the said mixture, removing the solution from the gas and blowing the solution with steam to drive oil the hydrogen sulfide, carbon dioxide and the like and recontaining the same which comprises washing the gas mixture in the absorption state with a solution of an alkali salt of dichlorphenate and free dichlorphenol for the removal of hydrogen sulfide, carbon dioxide and the like, removing the solution together with the thereby liberated chlorinated phenol and heating while blowing with steam to drive off hydrogen sulfide, carbondioxide and the like therefromand regenerating 4. A process for removing carbon dioxide and the absorbent properties of the solution. the like containing the same according to claim 3. A process for removing carbon dioxide from 2 in which the alkali salt of dichlor phenate is gas mixtures containing the same according to potassium dichlor phenate. claim 2 in which the alkali salt of dichlor phenate 5 I is sodium dichlor phenate, dnonan: L. m'mmson. 

